Apparatus for Coproducting ISO Type Reaction Products and Alcohols From Olefins, and Method for Coproducting Them Using The Apparatus

ABSTRACT

The present invention relates to an apparatus for coproducting iso-type reaction product and alcohol from olefin, and a method for coproducting using the apparatus, in which the hydroformylation reactor provides a sufficient reaction area due to the broad contact surface area between the olefin and the synthesis gases that are the raw materials by a distributor plate installed in the reactor, and the raw materials can be sufficiently mixed with the reaction mixture due to the circulation of the reaction mixture so that the efficiency of the production of the aldehyde is excellent; and also the hydrogenation reactor suppresses the side reaction so that the efficiency for producing aldehyde and alcohol are all increased, and also iso-type reaction product and alcohol can be efficiently co-produced.

TECHNICAL FIELD

The present invention relates to an apparatus for coproducting iso-typereaction products and alcohols from olefins, and a method forcoproducting them using the apparatus, and more specifically, to anapparatus for coproducting iso-type reaction products and alcohols fromolefins, and a method for coproducting them using the apparatus, inwhich the apparatus comprises a hydroformylation reactor;

a first main distillation column; a hydrogenation reactor; a foredistillation column; a second main distillation column; a postdistillation column; and a pipe for connecting them; in which any one ofthe first main distillation column and the second main distillationcolumn is operated during the reaction.

BACKGROUND ART

A hydroformylation reaction that is generally well known as OXO reactionis the process for producing a linear (normal) and branch-(iso)aldehyde, in which the olefin is added with one carbon atoms by reactall kinds of olefins and synthesis gases (CO/H ₂) in the presence of ametal catalyst and a ligand.

All kinds of aldehydes that are synthesized by OXO reaction are modifiedinto acids and aldehydes that are aldehyde derivatives, and alcoholsthrough an oxidation or a reduction reaction. Also, they can be modifiedinto various acids, aldehydes and alcohols comprising long alkyl groupthrough the oxidation or reduction reaction after a condensationreaction, such as aldol, and the like. Those aldehydes, alcohols, andacids are being used as a raw material for solvents, additives, andplasticizers.

The representative example of hydroformylation is to produce octanol(2-ethylhexanol) from propylene using a rhodium based catalyst. Octanolis mainly used as a raw material for PVC plasticizer, such as DOP(dioctyl phathalate), and also as an intermediate raw material forsynthetic lubricants, surfactants, and the like.

Propylene is injected with a catalyst into OXO reactor using synthesisgases (CO/H₂) to produce normal-butylaldehydes and iso-butylaldehydes.The produced aldehyde mixture is transferred to a separator along withcatalyst mixture to separate into hydrocarbon and catalyst mixture, andthen the catalyst mixture is circulated into the reactor and thehydrocarbon is transferred to a stripper. The hydrocarbon in thestripper is stripped by fresh synthesis gases to recover non-reactedpropylene and synthesis gases into OXO reactor and transferbutylaldehydes to a fractionation column thereby separatingnormal-butylaldehydes and iso-butylaldehydes, respectively.Normal-butylaldehydes of the fractionation column bottom is transferredto a hydrotreated reactor, and then adding hydrogen products n-butanol.Alternatively, normal-butylaldehydes are introduced into an aldolcondensation reactor to produce 2-ethylhexanal through a condensationand dehydration reaction, and then transferred to the hydrotreatedreactor to be octanol (2-ethylhexanol) by adding hydrogen.

The hydroformylation reaction may be performed in a continuous,semi-continuous or batch type, and a typical hydroformylation reactionis a gas or liquid circulation system. It is important for thehydroformylation reaction to increase the reaction efficiency bysmoothly contacting the starting materials that are composed of a liquidphase and gas phase. For this reason, conventionally the continuousstirred tank reactor (CSTR) that stirs for evenly contacting the liquidphase and the gas phase inside the reactor was mainly used. In addition,U.S. Pat. No. 5,763,678 discloses the hydroformylation method, in whichthe circulation is used instead of the stirring by applying the reactorthat is a type of loop. However, those methods have a limit to theimprovement of the hydroformylation reaction efficiency and also singlereactor cannot produce the satisfactory aldehyde product, so that theresidence time of the reaction is made to be longer, or more than tworeactors are connected in series thereby producing the product that hasa required level.

In addition, the hydrogenation process of aldehydes generally uses thereactor, in which nickel-based or copper-based solid hydrogenationcatalyst is filled inside the reactor. There are two ways for performingthe reaction, such that the starting aldehydes are evaporated to performthe reaction in a vapor phase, or the starting aldehydes are introducedinto the reactor as a liquid to perform the reaction in a liquid phase.

However, there is a problem that the selectivity of the reaction isreduced by generating an undesirable side reaction, such asesterification, acetal formation, etherification, and the like in theabove reaction, even though the above catalysts types, the vapor phase,or the liquid phase are applied.

DISCLOSURE OF INVENTION Technical Problem

In order to solve the conventional technical problems as mentionedabove, an object of the present invention provides an apparatus forcoproducting iso-type reaction products and alcohols from olefins, and amethod for coproducting them using the apparatus.

Solution to Problem

The present invention is to provide an apparatus for co-production ofiso-type reaction product and alcohol form olefin as one mean forsolving the above objects, in which the apparatus includes ahydroformylation reactor; a first main distillation column; ahydrogenation reactor; a fore distillation column; a second maindistillation column; a post distillation column; and a pipe forconnecting them, and only one of the first main distillation column andthe second main distillation column is operated.

As another mean for solving the above objects as mentioned above, thepresent invention provides a method for co-production of iso-typereaction product and alcohol from olefin, comprising: hydroformylatingfor obtaining aldehyde by reacting micro-bubbles and the catalyst mixedsolution while converting a spraying flow of olefin and the synthesisgases after forming the micro-bubbles of synthesis gases and olefin byspraying olefin and a synthesis gases (CO/H₂) in the catalyst mixedsolution by using the second main distillation column from the aboveapparatus;

discharging iso-type alcohol from the second main distillation columnthrough the fore distillation column by using the hydrogenation reactionproduct obtained by adding hydrogen to the normal-aldehyde andiso-aldehyde that are the hydroformylation products; and

discharging normal-type alcohol from the post distillation column.

As another mean for solving the above objects, the present inventionprovides a method for co-production of iso-type reaction product andalcohol from olefin, comprising:

hydroformylating for obtaining aldehyde by reacting the micro-bubblesand the catalyst mixed solution while converting a spraying flow ofolefin and the synthesis gases after forming the micro-bubbles ofsynthesis gases and olefin by spraying olefin and synthesis gases(CO/H₂) in the catalyst mixed solution by using the first maindistillation column from the above apparatus;

discharging iso-type aldehyde among the hydroformylation reactionproduct that is the product of the hydroformylation from the first maindistillation column; and

separating normal-type alcohol from the post column through the foredistillation column by using the hydrogenation reaction product that isthe product obtained by adding hydrogen to the normal-component that isthe residue of the main distillation column.

As another mean for solving the above objects as mentioned above, thepresent invention provides a method for co-production of iso-typereaction product and alcohol from olefin, comprising: hydroformylatingfor obtaining aldehyde by reacting the micro-bubbles and the catalystmixed solution while converting the spraying flow of the olefin and thesynthesis gases after forming the micro-bubbles of synthesis gases andolefin by spraying olefin and the synthesis gases (CO/H₂) in thecatalyst mixed solution by further using an aldol condensation kettle tothe first main distillation column among the above apparatus;discharging iso-type aldehyde among the hydroformylation reactionproduct that is the product obtained by the hydroformylation from thefirst main distillation column; producing aldehyde having an increasedcarbon atoms by the aldol condensation of the normal-component that is aresidue of the main distillation column; and separating alcoholcomponent having an increased carbon atoms from the post distillationcolumn through the fore distillation column by using the hydrogenationreaction product obtained by adding hydrogen to the aldehyde having anincreased carbon atoms that is the product obtained from the aldolcondensation.

Hereinafter, an apparatus for coproducing iso-type reaction products andalcohols from olefins according to an example of the present inventionwill be described in detail with reference to accompanying drawings.

Firstly, the term, iso-type reaction product, used for the presentinvention relates to a meaning including all of alcohol and iso-typealdehyde, and for example includes iso-butylaldehyde, iso-butanol, andthe like.

In addition, the term, alcohol, used for the present invention isalcohol not iso-type, and for example, includes normal-typenormal-butanol, 2-ethylhexanol, and the like.

FIG. 1 a roughly shows an apparatus for co-production of iso-typealdehyde and normal-type alcohol from olefin according to an embodimentof the present invention. The figure showing all of the pipes are notshown due to the expression.

The apparatus for producing iso-type aldehyde and normal-type alcoholfrom olefin according to an embodiment of the present invention is usedfor the reaction using a pipe in the following order: thehydroformylation reactor 1; the hydrogenation reactor 2; the foredistillation column 3; the second main distillation column 4′ and thepost distillation column 5.

The hydroformylation reactor 1 will be described in more detail asfollows. Any continuous stirred tank reactor or venturi-loop reactor ispreferably used as the hydroformylation reactor. Especially, it ispreferable that for the hydroformylation reactor, an early reactorshould be connected to a following reactor in series; but the reactiontemperatures of both reactors should be the same; and the reactionpressure in the early reactor should be higher than that of thefollowing reactor in terms of the efficiency of the reaction. When usingthe venturi-loop reactor, more preferably, the venture-loop reactorshould include a diffusion tube, a distributor plate, and a nozzlehaving a venture thereby improving the efficiency of the reaction.

The temperature in the reactor is 89° C.; when using two reactorsconnected in series, it is more preferable that an early pressure is 18bars and a following pressure 15 bars in terms of the efficiency of thereaction.

The olefin and the synthesis gases are sprayed in the catalyst mixedsolution charging inside the reactor by a mean for spraying that isinstalled on the top part of the reactor.

The mean for spraying is not limited in particular if it can spray theolefin and the synthesis gases in the catalyst mixed solution charginginside the reactor, but for example, an ejector having a nozzle can beused. The nozzle that is installed in the ejector has a role inincreasing speed by decreasing a cross-sectional area of spraying of theolefin and the synthesis gases that are supplied inside the reactor dueto the high pressure. The diameter of the nozzle may depend to the sizeof the reactor, and generally it is preferably 1 to 4 mm.

In addition, the ejector preferably combines a venturi tube. The venturitube includes a inlet part having a linear tube type as known and thediffusion tube having the structure that is becoming wider to its lowerpart, and the inlet part , through which the olefin and the synthesisgases are flowed, is combined to the ejector and the diameter of theinlet part is the same with the inlet diameter of the diffusion tube andsmaller than the outlet diameter of the diffusion tube. At the sametime, the outlet direction of the diffusion tube is preferably pointingin the lower part of the reactor.

The diameter of the inlet part is preferably 0.2 to 10 mm, and thelength of the divergent inlet is preferably 1/50 to ½ of the wholelength of the reactor. The diameter of the divergent inlet is the samewith that of the inlet part and the diameter of the divergent partoutlet is preferably 1.0 to 10 times longer than that of the divergentpart inlet. In addition, the length of the divergent part is preferably0.1 to 10 times longer than that of the inlet part, and the whole lengthof the venturi tube combined with the inlet part and the divergent partis preferably 0.01 to 0.95 times longer than that of the reactor bodyand most preferably 0.05 to 0.75 times.

The olefin and the mixture gases that are the raw materials for thereaction are sprayed inside the reactor through the ejector and theventuri tube combined the ejector and then while the olefin and themixture gas sprayed as mentioned above form the micro-bubbles, they aresprayed in the catalyst mixed solution charging inside the reactor.

The micro-bubbles of the olefin and the mixture gas are contacted to thecatalyst mixed solution so that it can provide a sufficient reactionarea due to a broad surface area for a gas-liquid contact.

In addition, the flow of the olefin and the mixture gas sprayed by thedistributor plate installed between the mean for sprayings and theoutlet of the reactor is converted. The retention time of the rawmaterial in the reactor is becoming longer due to the conversion of theflow of the raw material for the reaction thereby improving theefficiency of the reaction. The flow conversion of the raw material forthe reaction is determined according to the location and shape of thedistributor plate so that the efficiency of the reaction can becontrolled.

The distributor plate is preferably located between ⅓ and ⅔ of thelength up to the reactor outlet and venturi tube outlet in a directionof the venturi tube from the reactor outlet, and most preferably ½.Thesize of the distributor plate may be 10% to 75% of the inside diameterof the reactor.

As mentioned above, the hydroformylation reaction is proceeded whilespraying the olefin and the synthesis gases in the catalyst mixedsolution so that there is the reaction mixture containing the aldehyde,the catalyst mixed solution, non-converted olefin, the synthesis gases,other reaction by products, and the like in the reactor. The reactionmixture is collected in the lower part of the reactor by the circulationpipe connected to the outlet of the reactor and the mean for spraying,and then is supplied to the mean for spraying installed on the upperpart of the reactor. The reaction mixture is sprayed along with the rawmaterial for the reaction by the circulation and then the raw materialis sufficiently mixed with the reaction mixture so that the efficiencyof the reaction is improved. The circulation can be controlled by acirculation pump installed to the circulation pipe.

In addition, the circulation pipe may have a heat exchanger and may benot limited to a specific location on the circulation pipe. The reactionmixture separated in any one point of the circulation pipe of thehydroformylation reactor is separated to the catalyst mixed solution andthe aldehdye by catalyst/aldehyde separation part (not shown), and thenthe catalyst mixed solution is circulated to the hydroformylationreactor 1 and the aldehyde is transferred to the hydrogenation reactor2.

Hereinafter, the catalyst/aldehyde separation part (not shown) will bedescribed in more detail.

The catalyst/aldehyde separation part includes a separation pipe that isseparated from any one point of the circulation pipe of thehydroformylation reactor for separating the reaction mixture from thecirculation flow; a catalyst/aldehyde separation apparatus that isconnected to the separation pipe for separating the catalyst mixedsolution and the aldehyde from the reaction mixture; a catalyst mixedsolution supply pipe for supplying the catalyst mixed solution to thecirculation pipe by connecting to any one point of the catalyst/aldehydeseparation apparatus and the circulation pipe; and a aldehyde collectionpipe for collecting the aldehyde by connecting to the catalyst/aldehydeseparation apparatus.

The reaction mixture of the hydroformylation reactor 1 is separated fromany one point of the circulation pipe by the separation pipe of thecatalyst/aldehyde separation part and then supplied to thecatalyst/aldehyde separation apparatus. The catalyst mixed solutionseparated from the catalyst/aldehyde separation apparatus is circulatedto the hydroformylation reactor through the catalyst mixed solutionsupply pipe connected to any one point of the circulation pipe. Thealdehyde separated from the catalyst/aldehyde separation apparatus istransferred to the hydrogenation reactor through the aldehyde collectionpipe connected to the catalyst/aldehyde separation apparatus.

A kind of the catalyst/aldehyde separation apparatus is not limited ifit is a mean that is able to separate the catalyst mixed solution thealdehyde from the reaction mixture. For example, the aldehyde that is alow boiling point component among the reaction mixture is discharged ina vapor phase through the heat exchanging process and the catalyst mixedsolution that is a high boiling point component may use an evaporationapparatus that can discharge in a liquid phase.

The circulation of the catalyst mixed solution without the aldehyde thatis the object may be continuously performed. In some cases, a part ofthe circulated reaction mixture is discharged to regenerate catalyst orthe new catalyst solution or reactivated catalyst solution may be addedto the circulation flow of the reaction mixture.

The aldehyde separated from the catalyst/aldehyde separation part istransferred to the hydrogenation reactor 2 and is converted to thealdehyde and alcohol by the hydrogenation reaction.

The hydrogenation reactor 2 includes a mean for spraying for sprayingthe collected aldehyde and hydrogen gas to the catalyst mixed solutioncharged inside the reactor; a reactor outlet that is located on thelower part of the reactor for discharging the aldehyde and the hydrogengas, and the hydrogenation reaction mixture of aldehyde; and acirculation pipe that is connected to the reactor outlet and the meanfor spraying for collecting the aldehyde and the hydrogen gas, and thehydrogenation reaction mixture of aldehyde from the reactor outlet andthen supplying them to the mean for spraying to circulate them. Thehydrogenation reactor may include a loop reactor or a dual fixed-bedreactor. Especially, the reaction condition to the outlet of thehydrogenation reactor is appropriately 110° C. and 25 bars.

The hydrogenation reaction mixture of aldehyde, and the aldehyde andhydrogen gas are sprayed in the catalyst mixed solution charged insidethe reactor by the mean for spraying.

The mean for spraying may use the ejector installed with the nozzle. Thenozzle that is installed in the ejector has a role in increasing speedby decreasing a cross-sectional area of spraying of the olefin and thesynthesis gases that are supplied inside the reactor due to the highpressure.

The diameter of the nozzle may depend to the size of the reactor, andgenerally it is preferably 1 to 4 mm.

In addition, the ejector preferably combines a venturi tube. The venturitube includes a inlet part and the diffusion tube, the inlet part iscombined to the ejector, and the diameter of the inlet part is the samewith the inlet diameter of the diffusion tube, and smaller than theoutlet diameter of the diffusion tube. At the same time, the directionof the divergent part 122 b outlet is preferably toward the bottom ofthe reactor. The diameter of the inlet part is preferably 0.2 to 10 mm,the diameter of the divergent inlet is the same with that of the inletpart and the diameter of the divergent outlet is preferably 1.0 to 10times longer than the diameter of the divergent inlet. The length of thediffusion tube is preferably 0.1 time to 1 time the length of the inletpart, and the length of the whole venturi tube combining the inlet partand the diffusion tube is more preferably 0.01 time to 0.95 time thebody length of the reactor.

The hydrogenation reaction mixture of the aldehyde, and the aldehyde andthe hydrogen gas are sprayed inside the reactor through the ejector andthe venturi tube combined the ejector and then while the aldehyde andthe hydrogen gas sprayed as mentioned above form the micro-bubbles, theyare sprayed in the catalyst mixed solution charging inside the reactor.The micro-bubbles of the aldehyde and the hydrogen gas are contacted tothe catalyst mixed solution so that it can provide a sufficient reactionarea due to a broad surface area for a gas-liquid contact. For thisreason, the efficiency of the hydrogenation reaction of the aldehyde isimproved.

The aldehyde and the hydrogen gas that are sprayed inside the reactorare reacted under presence of the catalyst mixed solution to produce thealdedyde and the alcohol that are the reaction products. For thisreason, there are the aldehyde, the alcohol, the hydrogen, the reactionby-product, and the catalyst mixed solution in the reactor. Thehydrogenation reaction mixture is collected in the lower part of thereactor and then supplied to the mean for spraying at the upper part ofthe reactor by the circulation pipe connected to the outlet of thereactor and the mean for spraying. While the hydrogenation reactionmixture is sprayed along with the raw material of the reaction accordingto the above circulation, the hydrogenation reaction mixture issufficiently mixed with the raw material thereby improving theefficiency of the reaction. The circulation can be controlled by thecirculation pump installed in the circulation pipe.

In addition, the circulation pipe may include the heat exchanger and thelocation of the heat exchanger is not limited to a specific location onthe circulation pipe. The heat exchanger has a role in maintaining thehydrogenation reaction mixture circulated to the reactor to have asuitable temperature for the hydrogenation reaction.

The catalyst mixed solution charged in the reactor is a field containingnickel or copper, and will be described later.

In addition, the hydrogenation reaction mixture that is separated fromany one point of the circulation pipe is separated to the catalyst mixedsolution, the aldehyde, and the alcohol in the catalyst mixed solution,the aldehyde, and the alcohol separation apparatus; the separatedcatalyst mixed solution is circulated to the hydrogenation reactorthrough the catalyst mixed solution supply pipe connected to any onepoint of the circulation pipe; and then the hydrogenation reactionmixture may be transferred to the distillation apparatus part containingthe aldehyde and the alcohol.

Alternatively, the hydrogenation reactor 2 may include the mean forspraying for spraying the aldehyde and the hydrogen gas collected insidethe reactor; a nickel catalyst layer having high activity that islocated to the point entering the aldehyde and the hydrogen; and theoutlet of the reactor that is located at a point passing the coppercatalyst layer for discharging the hydrogenation reaction mixture.

The aldehyde and the hydrogen gas are sprayed inside the reactor by themean for spraying. The aldehyde and hydrogen sprayed are passed thenickel catalyst layer having a high activity and the copper catalystlayer having a low activity in order, and while passing them, thehydrogen is added to the aldehyde to produce the aldehyde and thealcohol.

Generally, the hydrogenation reaction of the aldehyde uses singlecatalyst of nickel or copper, but the present invention uses two-layercatalyst of nickel and copper. Generally, when using only nickelcatalyst having a high activity, the temperature is increased due to anexothermic reaction thereby increasing the temperature to the outlet ofthe reactor so that a side reaction will be generated. There is adisadvantage such that the side reaction is generated rather than theincrease of the efficiency of the reaction due to the catalyst having ahigh activity. Therefore, the present invention uses the nickel catalysthaving a high activity to the inlet of the reactor that has a highconcentration of the reactant to be converted so that the reaction speedis increased; and uses the copper catalyst layer having a low activityto the outlet of the reactor that has a low concentration of thereactant to be converted so that the side reaction is suppressed.

The aldehyde and the hydrogen gas sprayed inside the reactor produce thealdehyde and the alcohol that are the reaction product while passingthrough the two-layer catalyst layer. The hydrogenation reaction productcontaining the aldehyde and the alcohol passed through the hydrogenationreactor 2 is fractionally distilled.

The fractional distillation is performed at the distillation apparatuspart including the fore distillation column; the second maindistillation column; and the post distillation column. The distillationapparatus part is a distillation tower or distillation column type, andpreferably a type used in the art, generally.

The inlet part and each outlet of the distillation apparatus part aredivided, and the division wall is designed to insulate so that thetemperature and the pressure in the inlet part and each outlet can becontrolled, separately. The hydrogenation reaction product passedthrough the hydrogenation reactor includes the aldehyde, the alcohol,the hydrogen, the reaction by-product, and the like, and each materialis fractionally distilled according the boiling point.

The inlet part is preferably operated at the temperature of 20 to 1° C.and the pressure of 1.0 to 5.0 bars. The conditions for distillation ofthe hydrogenation reaction product in the inlet part are not limited,especially, and may be set to obtain the desired results considering avolatility of the product, a heat stability of the products, avolatility of the catalyst component, and a heat stability of thecatalyst component. However, the conditions are generally selected suchthat the temperature is in the range of 50 to 200° C. and the pressureis in the range of 1.00 mmHg to 1 MPa.

As shown a flow chart of FIG. 2, FIG. 1( a) of the present inventionprovides the method for co-production of iso-type reaction product andalcohol from olefin, comprising hydroformylating for obtaining thealdehyde by reacting the micro-bubbles and the catalyst mixed solutionwhile converting the spraying flow of the olefin and the synthesis gasesafter the micro-bubbles of the olefin and the synthesis gases byspraying the olefin and the synthesis gases (CO/H₂) in the catalystmixed solution using the second main distillation column 4′ among theabove mentioned apparatus; discharging iso-type alcohol from the secondmain distillation column through the fore distillation column using thehydrogenation reaction product obtained by adding hydrogen to thenormal-aldehyde and iso-aldehyde that are the product obtained from thehydroformylation reaction; and discharging the normal-type alcohol fromthe post distillation column.

Meanwhile, the hydroformylation is to obtain the aldehyde by reactingthe micro-bubbles and the catalyst mixed solution while converting thespraying flow of the olefin and the synthesis gases after forming themicro-bubbles of the olefin and the synthesis gases by spraying theolefin and the synthesis gases (CO/H₂) inside the catalyst mixedsolution.

While the olefin and the synthesis gases are sprayed, the micro-bubblesare formed and contacted to the catalyst mixed solution so that thesufficient reaction area can be provided due to the broad surface areaof the gas-liquid contact. In addition, the reaction is performed whileconverting the spraying flow of the olefin and the synthesis gases sothat the retention time of the raw materials for the reaction in thereactor is becoming longer and then the efficiency of the reaction canbe improved.

The hydroformylation is preferably performed using the hydroformylationapparatus part 1 as mentioned above.

The catalyst mixed solution in the hydroformylation reaction isgenerally used for the hydroformylation reaction, and may include atransition metal catalyst and ligand.

The transition metal catalyst can be used without limitation if it canbe generally used in the art, and for example, catalyst having atransition metal as a central metal, such as cobalt (Co), rhodium (Rh),iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium(Pd), iron (Fe), nickel (Ni), and the like, can be used. Specifically,more than one complex catalyst selected from the group consisting ofcobaltcarbonyl [Co₂(CO)₈], acetylaceton atodicarbonylrhodium[Rh(AcAc)(CO)₂], acetylacetonatocarbonylphenylphosphinerhodium[Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine)-rhodium[HRh(CO)(TPP)₃], acetylacetonatodicarbonyliridium [Ir(AcAc)(CO)₂] andhydridocarbonyltri(triphenylphosphine)-iridium[HIr(CO)(TPP)₃] can beused.

In addition, three-substituted phosphine, phosphine oxide, amine, amide,iso-nitrile, and the like can be used as ligand, and thethree-substituted phosphine can be preferably used. Thethree-substituted phosphine includes triaryl phosphine,triarylphosphate, alkylarylphosphine, and the like, but is not limitedthereto. More specifically, triphenylphosphine, tritolylphosphine,triphenylphosphate, n-butylphenylphosphine, and the like can be used.

A solvent used for the catalyst mixed solution may include for example,aldehydes, such as propane aldehyde, butyl aldehyde, pentyl aldehyde,valer aldehyde, and the like; ketones, such as acetone, methyl ethylketone, methyl isobutyl ketone, ace-tophenone, cyclohexanone, and thelike; alcohols, such as ethanol, pentanol, octanol, thenol, and thelike; aromatic type, such as benzene, toluene, xylene, and the like;ethers, such as tetrahydrofuran, dimethoxyethane, dioxane, and the like;and paraffin hydrocarbons, such as heptane, and the like; but is notlimited thereto. Propane aldehyde, butyl aldehyde, pentyl aldehyde,valer aldehyde, and the like that are the reaction products can bepreferably used.

In addition, for the concentration of the catalyst mixed solution, theweight of the relevant solvent preferably is 30% to 99% ratio of totalsolution weight.

The olefin that can be used for the present invention includes theolefin having 2 to 20 carbon atoms, but is not limited thereto; morespecifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undencene, 1-tridecene,1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene,1-nonadecene, 1-eicocene, 2-butene, 2-methylpropene, 2-pentene,2-methylbutene, 2-hexene, 2-heptene, 2-ethylhexene, 2-octene, styrene,3-phenyl-1-propene, 4-isopropylstyrene, and the like. Ethylene,propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 2-methylbutene, andthe like are more preferably used as the olefin that can be used for thepresent invention.

The synthesis gases that is another starting material for thehydroformylation reaction is the mixture gas of carbon monoxide andhydrogen, and the mix ratio of CO:H2 is preferably 5:95 to 70:30, morepreferably 40:60 to 60:40, and most preferably 45:55 to 55:45, but isnot limited thereto.

The mole ratio of the olefin and the synthesis gases is preferably 95:5to 5:95, and more preferably 75:25 to 25:75.

In addition, the olefin and the synthesis gases are preferably sprayedin the pressure of 5 to 200 bars, respectively. In addition, the linearvelocity for spraying the olefin and the synthesis gases is preferably 1msec to 50 msec, and more preferably 5 msec to 30 msec. The pressuredifference between before and after passing the catalyst mixed solutionthrough the mean for spraying 120 is preferably 0.1 bar to 10 bars, andmore preferably 0.5 bar to 5 bars.

The reaction is preferably performed at the temperature of 50 to 200 °C. and more preferably 50 to 150 ° C. In addition, the reaction ispreferably at the pressure of 5 bars to 100 bars, and more preferably 5bars to 20 bars.

In addition, preferably the step for hydroformylating further includesthe step for circulating the reaction mixture after collecting thereaction mixture to supply the olefin and the synthesis gases altogetherin the catalyst mixed solution.

The reaction mixture discharged through the outlet of the reactor 1 iscollected, and the reaction mixture is sufficiently mixed with the rawmaterial by the circulation system (shown in FIG. 1( a)) supplied insidethe reactor 1 so that the efficiency of the reaction is improved. Thereaction mixture includes the non-converted olefin, the reactionby-product, the catalyst mixed solution, and the like in addition to thealdehyde (normal-butylaldehyde and iso-butylaldehyde) that are thedesired objects.

The circulation system can be achieved by the circulation pipes combinedto the mean for spraying of the reactor and the outlet of the reactor 1,and the circulation pump combined to the circulation pipe. The flowamount of the circulated reaction mixture is preferably 0.01 to 20 timesthe volume charged in the reactor per minute.

In addition, the step for hydroformylating may further include the stepsfor separating the catalyst mixed solution and the aldehyde afterseparating a part of the circulated reaction mixture, supplying theseparated catalyst mixed solution to the circulation flow, andcollecting the aldehyde.

Specifically, when the olefin that is the starting material of thehydroformylation reaction is propylene, the reaction mixture includesbutyl aldehyde, more specifically normal-bytylaldehyde andiso-butylaldehyde. The reaction mixture is sent to the catalyst/aldehydeseparation apparatus to separate into the aldehyde and the catalystmixture. And then, the catalyst mixture is circulated to the reactor,and when not producing depending on the iso-type aldehyde, the aldehydecomponent is transferred to the reaction step in the fore distillationcolumn after hydrogenating.

Among the above steps, the hydrogenation step is the step for obtainingthe hydrogenation reaction product containing the aldehyde and thealcohol by adding hydrogen to the aldehyde that is the product obtainedfrom the hydroformylation step. A method for hydrogenating the aldehydecan use one that can be generally used in the art, but is preferablyperformed as follows.

The step for hydrogenating is preferably performed such that themicro-bubbles of the aldehyde and the hydrogen gas are formed byspraying the collected aldehyde and hydrogen gas inside the catalystmixed solution, and the micro-bubbles and the catalyst mixed solutionare reacted.

The catalyst mixed solution preferably includes Raney-Ni or copperpowder. The catalyst mixed solution can be used, and the aldehyde oraldehyde and alcohol is preferably used as a proper solvent.Specifically, the olefin that is the starting material forhydroformylating is propylene so that the normal- or iso-butylaldehyde,and the alcohol are preferably used as the solvent when the materialthat is introduced to the hydrogenation reactor is butylaldehyde. Thecomposite of the relevant solvent is preferably 2% to 99% and morepreferably 20% to 90% based on the weight ratio.

In addition, the hydrogenation of the aldehyde is preferably performedby passing the collected aldehyde and hydrogen gas through the catalystlayer consisting dual layers of Ni catalyst layer having a high activityand Cu catalyst layer having a low activity in order.

The hydrogenation of the aldehyde generally uses a single catalyst, suchas nickel or copper, but the present invention is characterized suchthat the catalyst layer consisting dual layers of nickel and copper isused. The dual catalyst layer pass the aldehyde and hydrogen gas in afluidized bed as a fixed bed.

Generally, when using only nickel catalyst having a high activity, theside reaction is generated due to raise the temperature to the outlet ofthe reactor because the temperature is increased by the exothermicreaction. There is a problem due to the generation of the side reactionrather than the increase of the efficiency of the reaction by thecatalyst having a high activity.

Therefore, the present invention is characterized such that the nickelcatalyst layer having a high activity is used to increase the reactionvelocity at the initial reaction, in which the concentration of thereactant should be converted is high, but the copper catalyst layerhaving a low activity is used to suppress the side reaction at the latereaction, in which the concentration of the reactant that should beconverted is low.

The aldehyde for hydrogenating is due to the hydroformylation of theolefin, and preferably includes more than one aldehyde group and 1 to 20carbons, but is not limited thereto. For example, there areformaldehyde, acetaldehyde, propion aldehyde, n-butyl aldehyde,iso-butylaldehyde, n-valeraldehyde, iso-valeraldehyde, n-hexaaldehyde,n-heptaaldehyde, n-octanal, 2-ethylhexanal, 2-ethylhexenal, n-decanal,2-ethylbutanal, propargylaldehyde, acrolein, glyoxal, crotonaldehyde,furfural, aldol, hexahydrobenzaldehyde, alpha-citronellal, citral,chloral, trimetylacetaldehyde, dietylacetaldehyde, tetrahydrofurfural,phenylaldehyde, cinnamaldehyde, hydrocinnamaldehyde, and the like.Preferably, there is propionaldehyde, n-butylaldehyde, iso-butylaldehydeor n-valeraldehyde and iso-valeraldehyde.

For example, when the hydroformylation reaction is proceeded usingpropylene, the normal-butylaldehyde and iso-butylaldehyde are produced.From among these, when the direction is to not produce depending oniso-type aldehyde, the hydrogenation and the reaction in the foredistillation column are performed, and when the direction is to producedepending on iso-type alcohol, the isobutylalcohol is discharged throughthe reaction in the second main distillation column and the normal-butylalcohol is discharged through the reaction in the post distillationcolumn.

The aldehyde is preferably sprayed in the velocity of 0.1 to 1 msec.While the aldehyde is sprayed in a certain velocity, the hydrogen issucked into the hydrogenation reactor 2.

For example, in case of when the hydroformylation reaction proceeds bypropylene, the normal-butylaldehyde and iso-butylaldehyde are generated.From among these, when the direction is to produce depending on iso-typealdehyde, the iso-butylaldehyde is discharged from the reaction in thefirst main distillation column, and when the direction is to producedepending on the alcohol increasing carbon atoms, the remainednormal-butylaldehyde produces 2-ethylhexanal by the aldol condensation.The octanol (2-ethylhexanol) can be produced by performing the reactionsin the hydrogenation and fore distillation column and the reaction inthe post distillation column by using the aldehyde increasing carbonatoms.

The mole ratio of the aldehyde and the hydrogen gas is preferably 1:10to 10:1. Preferably, the reaction temperature is 50 to 2° C. and thereaction pressure is 2 to 1 bar.

And then, the step for separating the structure isomer of alcohol andthe aldehyde is performed by fractionally distillation of thehydrogenation reaction product.

The hydrogenation reaction product includes the aldehyde, the hydrogen,the reaction by-product, and the like as well as the aldehyde andalcohol that are the desired objects. A method for separating thealdehyde and alcohol that are the desired objects can use the methodsthat are generally used in the art, but preferably use the followingmethods.

The fractional distillation 3 may use the column having the regionsdivided by the division wall. The division wall is designed to beinsulated, and the temperature and pressure in each divided region maybe individually different from the operation temperature and pressure ofthe column that is traditionally used according to the location andstructure of the divided region, and may be suitably controlledaccording to the plan. The hydrogenation reaction product isfractionally distillated according to the boiling point while passingthrough each divided region.

The normal- and iso-aldehyde, water, alcohol, and the like that are thelow boiling point components among the hydrogenation reaction productsare evaporated in the divided region controlled by the relative lowtemperature and pressure, and then discharged into the upper part of thecolumn. In addition, the iso-aldehyde and alcohol, and thenormal-aldehyde and alcohol that are the middle boiling point componentsare not evaporated or liquefied during the evaporation to discharge fromthe middle boiling point region of the column.

For example, when the hydroformylation reaction is performed by usingpropylene, the normal-butylaldehyde and iso-butylaldehyde are generated,and the normal-butylalcohol and iso-butylalcohol are finally obtainedthrough the hydrogenation and fore distillation purification steps, thesecond main distillation purification step, and the post distillationpurification step in order. The separation operation can be generallyperformed by the distillation operation, such as simple distillation,rectification, thin film distillation, vapor distillation, and the like.

The conditions for distillation are not limited, especially, and may beset to obtain the desired results considering a volatility of theproduct, a heat stability of the products, a volatility of the catalystcomponent, and a heat stability of the catalyst component. However, theconditions are generally selected such that the temperature is in therange of 50 to 200 ° C. and the pressure is in the range of 1.00 mmHg to1 MPa.

It can be determined through the following Examples that the normal-typealcohol and iso-type alcohol are contented with the range of 1:1 to 15:1that is N/I selection ratio under the catalyst combinations of one ofRh/TPTP (tri-p-tollylphosphine), Rh/TMPP (tri-m-tollylphosphine),Rh/TOTP (tri-o-tollylphosphine), Rh/CHDP (cyclohexyldiphenylphosphine)Rh/TmPP (trimethoxyphenylphosphine), and Rh/TePP(triethoxyphenylphosphine).

In addition, it is also confirmed through the following Examples thatthe normal-type alcohol and iso-type alcohol are contented with therange of 8:1 to 12:1 that is N/I selection ratio under Rh/TPP(triphenylphosphine) catalyst.

Meanwhile, it is more preferably in terms of the reaction efficiencythat a supply velocity F_(PPY)(mol/hr) of the olefin to the reaction, aproduction velocity F_(IBO)(mol/hr) of the isobutanol, and a productionvelocity F_(NBO)(mol/hr) of the normal-butanol are contented with thefollowing Equation Ito Equation III under the catalyst combinations ofany one of Rh/TPTP, Rh/TMTP, Rh/TOTP, Rh/CHDP, Rh/TmPP, and Rh/TePP:

2.4≦F_(PPY)/F_(IBO)≦19.2   (I)

1.3≦F_(PPY)/F_(NBO)≦2.4   (II)

1.0≦F_(NBO)/F_(IBO)≦15.0   (III)

In addition, it is more preferably that the supply velocityF_(PPY)(mol/hr) of the olefin to the reaction, the production velocityF_(IBO)(mol/hr) of the isobutanol, and the production velocityF_(NBO)(mol/hr) of the normal-butanol are contented with the followingEquation I′ to Equation III′ under Rh/TPP catalyst combination:

10.8≦F_(PPY)F_(IBO)≦15.6   (I′)

1.2≦F_(PPY)/F_(NBO)≦1.5   (II′)

8.0≦F_(NBO)/F_(IBO)≦12.0   (III)

Meanwhile, other order of the present invention is as follows: thehydroformylation reactor 1; the first main distillation column 4; thehydrogenation reactor 2; the fore distillation column 3; and the postdistillation column 5 in order so that the first main distillationcolumn 4 can be used as shown in the accompanying FIG. 1 b.

Using the above apparatus, as shown in the flow chart of FIG. 2, thepresent invention provides the method for co-production of iso-typereaction product and alcohol from olefin, comprising:

hydroformylating for obtaining aldehyde by reacting the micro-bubblesand the catalyst mixed solution while converting the spraying flow ofthe olefin and the synthesis gases after forming the micro-bubbles ofthe olefin and the synthesis gases by spraying the olefin and thesynthesis gases (CO/H₂) in the catalyst mixed solution;

discharging the iso-type aldehyde among the hydroformylation reactionproducts that are the products obtained from the hydroformylationreaction from the first main distillation column; and

separating normal-type alcohol from the post column through the foredistillation column by using the hydrogenation reaction product that isthe product obtained by adding hydrogen to the normal-component that isthe residue of the hydrogenation reaction product.

For example, when the hydroformylation reaction is proceed by usingpropylene, the normal-butylaldehyde and iso-butylaldehyde are produced,and when the direction is to produce depending on the isoaldehyde, theiso-butyl aldehyde among these is discharged through the reaction in thefirst main distillation column and the remained normal-butylaldehydeproduces the normal-butanol by the hydrogenation and further fractionaldistillation process.

The process conditions, the reaction apparatus, and used materialaccording to each step are the same as the mentioned above.

Moreover, it is more preferably in terms of the reaction efficiency thatthe supply velocity F_(PPY)(mol/hr) of the olefin to the reaction, theproduction velocity F_(IBO)(mol/hr) of the isobutylaldehyde, and theproduction velocity F_(NBO)(mol/hr) of the normal-butanol are contentedwith the following Equation IV to Equation VI under the catalystcombinations of any one of Rh/TPTP, Rh/TMTP, Rh/TOTP, Rh/CHDP, Rh/TmPP,and Rh/TePP:

2.4≦F_(PPY)/F_(IBA)≦19.2   (IV)

1.3≦F_(PPY)/F_(NBO)≦2.4   (V)

1.0≦F_(NBO)/F_(IBA)≦15.0   (VI)

Meanwhile, it is more preferably that the supply velocityF_(PPY)(mol/hr) of the olefin to the reaction, the production velocityF_(IBO)(mol/hr) of the isobutylaldehyde, and the production velocityF_(NBO)(mol/hr) of the normal-butanol are contented with the followingEquation IV′ to Equation VI′ under Rh/TPP catalyst combination:

10.8≦F_(PPY)/F_(IBA)≦15.6   (IV′)

1.2F_(PPY)/F_(NBO)≦1.5   (V′)

8.0≦F_(NBO)/F_(IBA)≦12.0   (VI′)

Moreover, another order of the present invention is as follows: thehydroformylation reactor 1; the first main distillation column 4; thealdol condensation reactor 6; the hydrogenation reactor 2; the foredistillation column 3; and the post distillation column 5 in order sothat the aldol condensation reactor 6 can be further included to thefirst main distillation column 4 as shown in the accompanying FIG. 1 c.The reaction conditions for the aldol condensation reaction arepreferably at 1° C. and 2 bars. As the reactor used for the abovesituation, a continuous stirred-tank reactor (CSTR) charging with NaOHcatalyst aqueous solution is effective but is not limited thereto.

Using the above apparatus, as shown in the flow chart of FIG. 2, thepresent invention provides the method for co-production of iso-typereaction product and alcohol from olefin, comprising: hydroformylatingfor obtaining aldehyde by reacting the micro-bubbles and the catalystmixed solution while converting the spraying flow of the olefin and thesynthesis gases after forming the micro-bubbles of the olefin and thesynthesis gases by spraying the olefin and the synthesis gases (CO/H₂)in the catalyst mixed solution; discharging the iso-type aldehyde amongthe hydroformylation reaction products that are the products obtainedfrom the hydroformylation reaction from the first main distillationcolumn; producing aldehyde increasing carbon atoms by aldol condensationof the normal-component that is the residue of the main distillationcolumn; and separating alcohol component increasing carbon atoms fromthe post distillation column through the fore distillation column byusing the hydrogenation reaction product that is the product obtained byadding hydrogen to the aldehyde increasing carbon atoms that is theproduct obtained from the aldol condensation step.

As mentioned above, when using the aldol condensation reactor 6 afterthe first main distillation column 4, the aldehyde and alcoholincreasing two times the carbon atoms than that of the aldehyde producedafter the hydroformylation reactor can be produced.

For example, when the hydroformylation reaction is proceeded by usingpropylene, the normal-butylaldehyde and iso-butylaldehyde are produced;when the direction is to produce according to the iso-type aldehyde, theiso-butylaldehyde among these is discharged from the reaction in thefirst main distillation column, and when the direction is to produceaccording to the alcohol increasing carbon atoms, the remainednormal-butylaldehyde produces 2-ethylhexanal by the aldol condensation.The octanol (2-ethylhexanol) can be produced by performing the reactionsin the hydrogenation and fore distillation column and the postdistillation column by using the aldehyde increasing carbon atoms.

The process conditions, the reaction apparatus, and the used materialsaccording to each of steps are the same with the mentioned above.

Moreover, it is more preferably in terms of the reaction efficiency thatthe supply velocity F_(PPY)(mol/hr) of the olefin to the reaction, theproduction velocity F_(IBO)(mol/hr) of the isobutylaldehyde, and theproduction velocity F_(NBO)(mol/hr) of the 2-ethylhexanol are contentedwith the following Equation VII to Equation IX under the catalystcombinations of any one of Rh/TPTP, Rh/TMTP, Rh/TOTP, Rh/CHDP, Rh/TmPP,and Rh/TePP:

2.4≦F_(PPY)/F_(IBA)≦19.2   (VII)

2.6F_(PPY)/F_(EHO)≦4.8   (VIII)

0.5≦F_(EHO)/F_(IBA)7.5   (IX)

Meanwhile, it is more preferably that the supply velocity F_(PPY)(mol/hr) of the olefin to the reaction, the production velocityF_(IBO)(mol/hr) of the isobutylaldehyde, and the production velocityF_(NBO)(mol/hr) of the 2-ethylhexanol are contented with the followingEquation VII′ to Equation IX′ under Rh/TPP catalyst combination:

10.8≦F_(PPY)/F_(IBA)≦15.6   (VII′)

1.4≦F_(PPY)/F_(EHO)≦2.7   (VIII′)

4.0≦F_(EHO)/F_(IBA)≦6.0   (IX′)

Advantageous Effects of Invention

A hydroformylation reactor that is contained in an apparatus forcoproducing iso-type reaction products and alcohols from olefinsaccording to the present invention provides a sufficient reaction areadue to the broad contact surface of olefins and the synthesis gas thatare a raw material for reaction by a distributor plate that is installedinside the hydroformylation reactor and a sufficient mixing between theraw materials and the reaction mixture according to the circulation ofthe reaction mixture so that the efficiency in term of production ofaldehydes is excellent. In addition, the hydrogenation reactor foraldehydes suppresses sub-reactions to improve the efficiency in term ofproduction of aldehydes and alcohols.

The apparatus for coproducing iso-type reaction products and alcoholsfrom olefins according to the present invention provides the improvedprocess as mentioned above to save costs for coproducing iso-typereaction products and alcohols from olefins and increase the efficiencyin terms of production of alcohols.

The present invention was explained in details around the specificexamples in the above sentence, but it can be understood by the personwho has general information in the art that various modifications andvariations can be possible within the range and the technical spirit ofthis present invention and those modifications and variations belong tothe attached claims.

BRIEF DESCRIPTION OF DRAWINGS

The above and other objects, features and advantages of the presentinvention will become apparent from the following description ofpreferred embodiments given in conjunction with the accompanyingdrawings, in which:

FIG. 1 shows a process chart roughly according to an embodiment of thepresent invention; (a) is the process for producing iso-type aldehydeand normal-type alcohol from olefin according to Example 1; (b) is theprocess for producing iso-type aldehyde and normal-type alcohol fromolefin according to Example 2; and (c) is the process for producingiso-type aldehyde and normal-type alcohol from olefin according toExample 3.

FIG. 2 is a flow chart summarized according to the reaction order of thepresent invention.

EXPLANATION FOR MARKS ACCORDING TO MAIN PARTS OF FIGURES

1: Hydroformylation reactor

2: Hydrogenation reactor

3: Fore distillation column

4: First main distillation column

4′: Second main distillation column

5: Post distillation column

6: Aldol condensation reactor

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail inlight of Examples and Comparative Examples.

The present invention may, however, be embodied in many different formsand should not be construed as being limited to the Examples set forthherein. Rather, these Examples are provided such that this disclosurewill be thorough and complete and will fully convey the concept of thepresent invention to those skilled in the art.

Firstly, each reactor used for the present invention was prepared asfollows:

Hydroformylation Reactor 1

Two loop reactors having 30 liters of volume were prepared, and then anozzle having a diameter of 5 mm, a venturi diffusion tube having adiameter of diffusion tube inlet of 10 mm, a diameter of diffusion tubeoutlet of 20 mm, and a length of diffusion tube of 30 cm was installedat the head part of each reactor. In addition, the distributor platehaving a flat shape of 70 mm diameter was fixed at the point of 200 mmfrom the lower outlet inside each reactor.

The circulation pump was installed outside the reactor to circulate thereaction solution in a fluid velocity of 20 liter per minute with thespraying nozzle of each reactor head, and the heat exchanger wasinstalled in the outside circulation line in two reactors to remove heatof reaction generated by the reaction. Two reactors were connected inseries, and an early reactor (not shown) that is a first reactor amongtwo reactors connected in series connected one among the circulationlines to a top of a following reactor and a controller (not shown) wasinstalled for continuously operating the early reactor at the certainliquid level.

The following reactor 1 that is a second reactor connected to the earlyreactor in series had the controller for continuously operating at thecertain liquid level by transferring the reaction mixture to theevaporation apparatus for separating aldehyde at any one of circulationlines of the reactor like the early reactor. The propylene and synthesisgases that are the raw materials can be supplied separately in each loopreactors connected in series as mentioned above.

By proceeding the reaction, the product from the following reactor 1 wasinjected to the hydrogenation reactor 2 along with hydrogen gas throughthe condenser; aldehyde was collected through the evaporation apparatus;remained catalyst solution was circulated to the early and followingreactors through a separated pump.

Hydrogenation Reactor 2

A hydrogenation reactor was prepared in a distillation column typehaving 8 cm diameter and 330 cm length; the nickel catalyst supported ingamma-alumina was filled up to 210 cm from 10 cm of top part; aluminaball was filled to 230 cm therefrom; and the copper catalyst supportedin gamma-alumina was filled to 320 cm therefrom to prepare thehydrogenation reactor 2.

The temperature of the reactor 2 outlet was maintained not over 110° C.and the inner pressure was maintained at 25 bar by using the separatedcirculation pump and outside heat exchanger.

Fore Distillation Column 3 and Post Distillation Column 5

A metal mesh (SUS mesh) and a rashig ring having 1 cm average diameterwere used for the fore distillation column 3 and the post distillationcolumn 5; a reboiler was installed at the lowest part of each column anda condenser and a reflux apparatus were installed at the top part.

First Main Distillation Column 4 and Second Main Distillation Column 4′

Two metallic pipes having 8 cm diameter and 148 cm length was prepared.

A metal mesh (SUS mesh) and a rashig ring having 1 cm average diameterwere used for the first distillation column 4 and the seconddistillation column 4′; a reboiler was installed at the lowest part ofeach column and a condenser and a reflux apparatus were installed at thetop part.

Aldol Condensation Reactor 6

A continuous stirred tank reactor (CSTR) having 30 liters was prepared.

Example 1 Preparation of n-BuOH and i-BuOH Applied with Rh/TPTP Catalyst

Step for Producing Catalyst Solution:

30.3 kg of normal-butylaldehyde having 99% purity and 1.6 kg of TPTP(tris-p-tollylphosphine) were injected and then completely dissolved.45.9 g of acetylacetoneitocarboyltirphenylphosphinerrhodium[Rh(AcAc)(CO)(TPP)](ROPAC) catalyst that was pre-quantified was furtherinjected to the above mixture to produce 32 kg of catalyst solution.

Step for Hydroformylation Reaction:

16 kg of ROPAC/TPTP catalyst solution that was prepared in advance wascharged into two hydroformylation reactors, respectively. After purgingwith nitrogen gas and propylene two times, respectively, the reactiontemperature was maintained at 89° C. through the circulation pump andoutside heat exchanger. When the temperature and pressure inside thereactor were stabilized, the propylene was injected until 12 barpressure inside each reactor.

And then, after stabilizing the temperature and pressure again,propylene that was the raw material was supplied to the early reactor in3.7 kg/hr flow velocity and the synthesis gases was supplied to theearly and following reactors in 2.2 kg and 0.5 kg average flow velocityper hour. The liquid level in each of reactors was maintained at 20liters; when it is stabilized such that the pressure and the temperaturein the early reactor were maintained at 18 bar and 89° C.; and then thepressure and the temperature in the following reactor were maintained at15 bar and 89° C., while the reaction product was continuously collectedin a certain flow velocity, the normal-operation was performed.

Steps for Hydrogenation Reaction and the Reaction in Fore DistillationColumn:

Firstly, for hydrogenation reaction and heat exchange, thenormal-butanol was used as an initial solvent medium at the initialreaction step, and the circulation flux was maintained at 38 kg perhour.

The reaction product containing the butyl aldehyde produced in thepreceding hydrofromylation reaction was supplied to the reactor 2 alongwith 0.26 kg hydrogen gas per hour. While maintaining the liquid level,the reaction composition was analyzed to reach the operation range ofthe normal-state.

Then while the reaction product produced from the hydrogenation reactionwas constantly supplied to the point of 20 cm from the top part of thefore distillation column 3, the low boiling point components wereremoved at the top part and the product of the lower part of the columnwas supplied to the second main distillation column 4′ by flowing toproduce depending on the iso-type alcohol.

Step for Discharging Product:

The supply to the second main distillation column 4′ as mentioned abovewas constantly supplied to the of 68 cm from the top part of the column,the iso-type alchol was collected from the top part and the product ofthe lower part of the column was introduced to the point of 25 cm fromthe top part of the post distillation column 5.

The normal type alcohol was collected from the top part of the postdistillation column 5, and the high boiling point component wascollected from the lower part of the column.

Type and Content of Collected Product:

After the reactions per each of steps reached to the normal-state asmentioned above, the operation time was total 92 hours; and 1.12 kg oflow boiling point component and less than 22 g of iso-butanol wereobtained into the top part of the fore distillation column 3 in thereaction. 116.8 kg of isobutanol and 1.6 kg of normal-butanol weretotally obtained as the product of the top part of the second maindistillation column 4′. In addition, as the product of the top part ofthe post distillation column 5, 468.6 kg of normal-butanol and less than1.0 kg of isobutanol were obtained; and as the product of the lower partof the column, 24 kg of heavy component, such as aldehyde trimer and 0.7kg of normal-butanol were obtained.

It can be confirmed in order to calculate N/I selection ratio that thevalue added with all of the normal-butanol weights obtained at the toppart of the second main distillation column 4′, and the top part and thelower part of the post distillation column 5 was divided by the valueadded with all of isobutanol weights obtained at the top part of thefore distillation column 3, the top part of the second main distillationcolumn 4′, and the top part of the post distillation column 5 gives 4.0.

The result for converting energy supplied to the column from thereboiler at the normal-state of operation condition to calory was 2.12MCal/hr; that is, the fore distillation column 3 was average 0.29 MCalper hour, the second main distillation column 4′ was 1.36 MCal, and thepost distillation column 5 was 0.47 MCal.

MODE FOR THE INVENTION Example 2 Production of i-BAL and n-BUOH by usingRh/TPTP Catalyst (1)

The same process with Example 1 was repeated, but Example 2 used theapparatus as shown in FIG. 1( b) and was performed according to the flowchart as shown in FIG. 2.

As a result, 112.5 kg isobutylaldehyde was obtained as the product ofthe top part of the first main distillation column 4 and 472.1 kgnormal-butanol was obtained from the top part of the post distillationcolumn 5.

Example 3 Production of i-BAL and 2-EH by using Rh/TPTP Catalyst (1)

The same process with Example 2 was repeated, but Example 3 used theapparatus as shown in FIG. 1( c) and was performed according to the flowchart as shown in FIG. 2.

20 liters solution mixed with 0.95% NaOH catalyst aqueous solution andthe product of the lower part containing normal-butyl aldehyde of themain distillation column 4 that was the preceding step in 1:1 ratio wascharged into the aldol condensation reactor 6 that was further used inthe present Example, and the temperature inside the reactor 6 wasmaintained at 1° C. and the pressure was maintained 2 bar.

That is, the product of the lower part of the column containing thenormal-butyl aldehdye of the first main distillation column 4 wascontinuously injected to maintain 20 liters of liquid level while thestirring number was maintained at 2 rpm; at the same time, 0.95% NaOHcatalyst aqueous solution was injected at the same weight ratio to thereactor 6; and the reaction product from the reactor 6 was injected tothe hydrogenation reactor 2 by using the same process with Example 2.

Through the final separation purification step, 483.5 kg of2-ethylhexylalcohol was obtained and 122.4 kg of isobutylaldehyde wasobtained from the top part of the first main distillation column 4.

Example 4 Production of i-BuOH and n-BuOH by using Rh/TPTP Catalyst

The continuous experiment was performed with the same method withExample 1 except injecting 0.8 kg TPTP of Example 1. As a result, 147.2kg of isobutanol (i-BuOH) and 438.1 kg of normal-butanol (n-BuOH) wereobtained. At this time, N/I selection ratio was 3.0.

Example 5 Production of i-BAL and n-BuOH by using Rh/TPTP Catalyst (2)

As a result for continuously operating the same method with Example 2except producing the catalyst by using the same method with Example 4,152.3 kg of isobutylaldehyde and 431.6 kg of normal-butanol (n-BuOH)were obtained.

Example 6 Production of i-BAL and 2-EH by using Rh/TPTP Catalyst (2)

As a result for continuously operating the same method with Example 3except producing the catalyst by using the same method with Example 4,151.2 kg of isobutylaldehyde and 447.1 kg of 2-ethylhexanol wereobtained.

Example 7 Production of i-BuOH and n-BuOH by using Rh/TMTP Catalyst

As a result for continuously operating the same method with Example 1except dissolving by injecting 2.1 kg TMTP (tri-m-tollylphosphine)having 99% purity instead of TPTP in the step for producing catalyst,79.8 kg of isobutanol and 490.3 kg of normal-butanol were obtained. N/Iselection ratio was 6.1.

Example 8 Production of i-BAL and n-BuOH by using Rh/TMTP Catalyst

As a result for continuously operating the same method with Example 2and producing the catalyst solution by using the same method withExample 7, 76.9 kg of isobutylaldehyde and 487.1 kg of normal-butanolwere obtained.

Example 9 Production of i-BAL and 2-EH by using Rh/TMTP Catalyst

As a result for continuously operating the same method with Example 3and producing the catalyst solution by using the same method withExample 7, 80.2 kg of isobutylaldehyde and 492.7 kg of 2-ethylhexanolwere obtained.

Example 10 Production of i-BuOH and n-BuOH by using Rh/TOTP Catalyst

As a result for continuously operating the same method with Example 1except dissolving by injecting 3.2 kg TOTP (tri-o-tollylphosphine)having 99% purity instead of TPTP in the step for producing catalyst,228.1 kg of isobutanol and 342.5 kg of normal-butanol were obtained. N/Iselection ratio was 1.5.

Example 11 Production of i-BAL and n-BuOH by using Rh/TOTP Catalyst

As a result for continuously operating the same method with Example 2and producing the catalyst solution by using the same method withExample 10, 223.1 kg of isobutylaldehyde and 340.9 kg of 2-ethylhexanolwere obtained.

Example 12 Production of i-BAL and 2-EH by using Rh/TOTP Catalyst

As a result for continuously operating the same method with Example 3and producing the catalyst solution by using the same method withExample 10, 235.7 kg of isobutylaldehyde and 346.1 kg of 2-ethylhexanolwere obtained.

Example 13 Production of i-BuOH and n-BuOH by using Rh/CHDP Catalyst

As a result for continuously operating the same method with Example 1except dissolving by injecting 1.06 kg CHDP(cyclohexyldiphenylphosphine) having 99% purity instead of TPTP in thestep for producing catalyst, 193.3 kg of isobutanol and 386.8 kg ofnormal-butanol were obtained. N/I selection ratio was 2.0.

Example 14 Production of i-BAL and n-BuOH by using Rh/CHDP Catalyst

As a result for continuously operating the same method with Example 2and producing the catalyst solution by using the same method withExample 13, 198.3 kg of isobutylaldehyde and 391.0 kg of normal-butanolwere obtained.

Example 15 Production of i-BAL and 2-EH by using Rh/CHDP Catalyst

As a result for continuously operating the same method with Example 3and producing the catalyst solution by using the same method withExample 13, 196.2 kg of isobutylaldehyde and 389.1 kg of 2-ethylhexanolwere obtained.

Example 16 Production of i-BuOH and n-BuOH by using Rh/TmPP Catalyst

As a result for continuously operating the same method with Example 1except dissolving by injecting 0.8 kg TmPP (trimethoxyphenylphosphine)having 99% purity instead of TPTP in the step for producing catalyst,169.1 kg of isobutanol and 422.3 kg of normal-butanol were obtained. N/Iselection ratio was 2.5.

Example 17 Production of i-BAL and n-BuOH by using Rh/TmPP Catalyst

As a result for continuously operating the same method with Example 2and producing the catalyst solution by using the same method withExample 16, 174.1 kg of isobutylaldehyde and 418.6 kg of normal-butanolwere obtained.

Example 18 Production of i-BAL and 2-EH by using Rh/TmPP Catalyst

As a result for continuously operating the same method with Example 3and producing the catalyst solution by using the same method withExample 16, 171.9 kg of isobutylaldehyde and 427.3 kg of 2-ethylhexanolwere obtained.

Example 19 Production of i-BuOH and n-BuOH by using Rh/TPP Catalyst

As a result for continuously operating the same method with Example 1except dissolving by injecting 3.2 kg TPP (triphenylphosphine) having99% purity instead of TPTP in the step for producing catalyst, 52.7 kgof isobutanol and 525.4 kg of normal-butanol were obtained. N/Iselection ratio was 10.0.

Example 20 Production of i-BAL and n-BuOH by using Rh/TPP Catalyst

As a result for continuously operating the same method with Example 2and producing the catalyst solution by using the same method withExample 19, 49.8 kg of isobutylaldehyde and 511.0 kg of normal-butanolwere obtained.

Example 21 Production of i-BAL and 2-EH by using Rh/TPP Catalyst

As a result for continuously operating the same method with Example 3and producing the catalyst solution by using the same method withExample 19, 51.2 kg of isobutylaldehyde and 509.8 kg of 2-ethylhexanolwere obtained.

As shown in Examples 1 to 6 used with the Rh/TPTP catalyst combination,Examples 7 to 9 used with Rh/TMTP catalyst combination, Examples 10 to12 used with Rh/TOTP catalyst combination, Examples 13 to 15 used withRh/CHDP catalyst combination, Examples 16 to 18 used with Rh/TmPP, andExamples 19 to 21 used with Rh/TPP, it could be confirmed that whenusing TPP, N/I selection ratio was improved to 10:1, and also when usingthe catalyst above TPP, N/I selection ratio was improved to 1.5 to 6.1.

1-9. (canceled)
 10. A method for coproducting iso-type reaction productand alcohol from olefin, comprising: hydroformylating for obtainingaldehyde by reacting micro-bubbles and the catalyst mixture solutionwhile converting the spraying flow of the olefin and the synthesis gasesafter forming the micro-bubbles of the olefin and the synthesis gases byspraying the olefin and the synthesis gases (CO/H₂) in the catalystmixture solution with using the second main distillation column of theapparatus according to claim 1; discharging iso-type alcohol from thesecond main distillation column through the fore distillation columnusing the hydrogenation reaction product obtained by adding hydrogen tothe normal-aldehyde and iso-aldehyde as the product obtained from thehydroformylation reaction; and discharging the normal-type alcohol fromthe post distillation column.
 11. A method for coproducting iso-typereaction product and alcohol from olefin, comprising: hydroformylatingfor obtaining aldehyde by reacting micro-bubbles and the catalystmixture solution while converting the spraying flow of the olefin andthe synthesis gases after forming the micro-bubbles of the olefin andthe synthesis gases by spraying the olefin and the synthesis gases(CO/H₂) in the catalyst mixture solution with using the first maindistillation column of the apparatus according to claim 1; dischargingiso-type aldehyde among the reaction product of hydroformylation fromthe first main distillation column wherein the reaction product ofhydroformylation that is the product from the hydroformylation reaction;and separating the normal-type alcohol from the post distillation columnthrough the fore distillation column by using the hydrogenation reactionproduct obtained by adding hydrogen to the normal-component as theresidue of the main distillation column.
 12. A method for coproductingiso-type reaction product and alcohol from olefin, comprising:hydroformylating for obtaining aldehyde by reacting micro-bubbles andthe catalyst mixture solution while converting the spraying flow of theolefin and the synthesis gases after forming the micro-bubbles of theolefin and the synthesis gases by spraying the olefin and the synthesisgases (CO/H₂) in the catalyst mixture solution with using the aldolcondensation reactor of the apparatus according to claim 8; dischargingiso-type aldehyde among the reaction product of hydroformylation fromthe first main distillation column wherein the reaction product ofhydroformylation that is the product from the hydroformylation reaction;producing the aldehyde having an increased carbon number byaldol-condensation of the normal-component as the residue of the maindistillation column; and separating the alcohol having an increasedcarbon number, from the post distillation column through the foredistillation column by using the hydrogenation reaction product obtainedby adding hydrogen to the aldehyde having an increased carbon number,that is the product of the aldol condensation reaction.
 13. The methodfor coproducting iso-type reaction product and alcohol from olefinaccording to any one of claim 10 to claim 12, wherein thehydroformylation step is performed by using the continuous stirred tankreactor or the venturi-loop reactor filled with the combination ofsolvent and the transition metal catalyst selected from the groupconsisting of rhodium (Rh), cobalt (Co), and iridium (Ir), and ligandselected from the group consisting of triphenylphosphine (TPP),tri-p-tollylphosphine (TPTP), tri-m-tollylphosphine (TMTP),tri-o-tollylphosphine (TOTP), cyclohexyldiphenylphosphine (CHDP),trimethoxyphenylphosphine (TmPP), triethoxyphenylphosphine (TePP),trimethylphosphine, triethylphosphine, tri-n-propylphosphine,tri-n-butylphosphine, tri-n-octylphosphine, tri-n-octadecylphosphine,n-octadecyldimethylphosphine, diethyl-n-octylphosphine, andethylmethyl-n-propylphosphine.
 14. The method for coproducting iso-typereaction product and alcohol from olefin according to any one of claim10 to claim 12, wherein the olefin is selected from the group consistingof ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-nonene,1-decene, 1-undencene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene,2-butene, 2-methylpropene, 2-pentene, 2-hexene, 2-heptene,2-ethylhexene, 2-octene, styrene, 3-phenyl-1-propene, and4-isopropylstyrene.
 15. The method for coproducting iso-type reactionproduct and alcohol from olefin according to claim 13, wherein the N/Iselectivity ratio of the normal alcohol and iso alcohol by using thecatalyst combination of one of Rh/TPTP, Rh/TMTP, Rh/TOTP, Rh/CHDP,Rh/TmPP, and Rh/TePP is in the range of 1:1 to 15:1.
 16. The method forcoproducting iso-type reaction product and alcohol from olefin accordingto claim 13, wherein the N/I selectivity ratio of the normal alcohol andiso alcohol by using Rh/TPP catalyst is in the range of 8:1 to 12:1.